The present invention generally relates to an environmentally benign and economically attractive catalytic process that allows preparation of value-added nitrogen compounds from readily available hydrocarbons.
Metal-mediated nitrene transfer reactions are fundamentally and practically important chemical processes that allow selective conversion of readily available hydrocarbons to synthetically and biologically valuable nitrogen-containing compounds via direct C—N bond formation. Using [N-(p-toluenesulfonyl)imino]phenyl iodinane (PhI=NTs) and related iminoiodane derivatives as the primary nitrene sources, significant progress has been made in both catalytic aziridination of alkenes and amination of C—H bonds.
Several limitations have been noted, however, with the use of iminoiodanes: commercial unavailability, high costly synthesis, short shelf life, insolubility in common solvents, and the generation of Arl as by-products. While the approach of in situ generation of iminoiodanes in the presence of terminal oxidants has met with enormous successes recently, alternative nitrene sources such as chloramine-T, bromamine-T, and tosyloxycarbamates have been actively pursued to improve catalytic nitrene transfer reactions
Azides represent a broad class of compounds that are considered ideal nitrene sources for metal-mediated nitrene transfer reactions. In addition to their wide availability and easy synthesis, azide-based nitrene transfers generate the chemically stable and environmentally benign nitrogen gas as the byproduct. Despite these advantages, only a few catalytic systems have been developed to catalyze the decomposition of azides for aziridination and amination effectively. Notable examples include Co(Por)-based amination with arylazides and Ru(Salen)-based aziridination with arylsulfonyl azides.